EP3580265A1 - Verfahren zum dispergieren von nanocellulose in organischen polymervorläufern - Google Patents
Verfahren zum dispergieren von nanocellulose in organischen polymervorläufernInfo
- Publication number
- EP3580265A1 EP3580265A1 EP18705382.2A EP18705382A EP3580265A1 EP 3580265 A1 EP3580265 A1 EP 3580265A1 EP 18705382 A EP18705382 A EP 18705382A EP 3580265 A1 EP3580265 A1 EP 3580265A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- cellulose
- epoxy
- nano
- water
- hardener
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000001913 cellulose Substances 0.000 title claims abstract description 68
- 229920002678 cellulose Polymers 0.000 title claims abstract description 67
- 238000000034 method Methods 0.000 title claims abstract description 46
- 239000002243 precursor Substances 0.000 title claims abstract description 11
- 229920000620 organic polymer Polymers 0.000 title description 2
- 239000004593 Epoxy Substances 0.000 claims abstract description 65
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000004814 polyurethane Substances 0.000 claims abstract description 18
- 229920001187 thermosetting polymer Polymers 0.000 claims abstract description 18
- 229920002635 polyurethane Polymers 0.000 claims abstract description 16
- 239000002131 composite material Substances 0.000 claims abstract description 14
- 239000000853 adhesive Substances 0.000 claims abstract description 11
- 150000001412 amines Chemical class 0.000 claims abstract description 11
- 230000001070 adhesive effect Effects 0.000 claims abstract description 10
- 238000000576 coating method Methods 0.000 claims abstract description 9
- 125000003700 epoxy group Chemical group 0.000 claims abstract description 9
- 239000012074 organic phase Substances 0.000 claims abstract description 9
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 8
- 239000000565 sealant Substances 0.000 claims abstract description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 24
- 239000002041 carbon nanotube Substances 0.000 claims description 24
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 24
- 239000000203 mixture Substances 0.000 claims description 24
- 239000004848 polyfunctional curative Substances 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 17
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 13
- 239000006185 dispersion Substances 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 229920001046 Nanocellulose Polymers 0.000 claims description 10
- 238000004821 distillation Methods 0.000 claims description 10
- 229920000642 polymer Polymers 0.000 claims description 10
- 239000000047 product Substances 0.000 claims description 10
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 8
- 239000000654 additive Substances 0.000 claims description 6
- 150000002009 diols Chemical class 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- 239000011248 coating agent Substances 0.000 claims description 5
- 239000012071 phase Substances 0.000 claims description 5
- 239000011347 resin Substances 0.000 claims description 5
- 229920005989 resin Polymers 0.000 claims description 5
- 238000002604 ultrasonography Methods 0.000 claims description 5
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical class C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 4
- 108700005457 microfibrillar Proteins 0.000 claims description 4
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 238000004132 cross linking Methods 0.000 claims description 3
- -1 defoamers Substances 0.000 claims description 3
- 125000005442 diisocyanate group Chemical group 0.000 claims description 3
- 239000000835 fiber Substances 0.000 claims description 3
- 239000012467 final product Substances 0.000 claims description 3
- 229920001228 polyisocyanate Polymers 0.000 claims description 3
- 239000005056 polyisocyanate Substances 0.000 claims description 3
- 229920005862 polyol Polymers 0.000 claims description 3
- 150000003077 polyols Chemical class 0.000 claims description 3
- 239000013538 functional additive Substances 0.000 claims description 2
- 125000003827 glycol group Chemical group 0.000 claims description 2
- 150000002894 organic compounds Chemical class 0.000 claims description 2
- 239000000049 pigment Substances 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 239000002114 nanocomposite Substances 0.000 abstract description 7
- 150000002334 glycols Chemical class 0.000 abstract description 2
- 239000007788 liquid Substances 0.000 abstract 1
- 238000009472 formulation Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000007790 solid phase Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000002121 nanofiber Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 241000905957 Channa melasoma Species 0.000 description 1
- 229920001410 Microfiber Polymers 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 206010037660 Pyrexia Diseases 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000013466 adhesive and sealant Substances 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 229940106691 bisphenol a Drugs 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 229940106135 cellulose Drugs 0.000 description 1
- 239000013530 defoamer Substances 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000013020 final formulation Substances 0.000 description 1
- 229910021485 fumed silica Inorganic materials 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 239000003658 microfiber Substances 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000002952 polymeric resin Substances 0.000 description 1
- 230000036647 reaction Effects 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/205—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase
- C08J3/2053—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase the additives only being premixed with a liquid phase
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/005—Reinforced macromolecular compounds with nanosized materials, e.g. nanoparticles, nanofibres, nanotubes, nanowires, nanorods or nanolayered materials
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/09—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/205—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/041—Carbon nanotubes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
- C08L1/02—Cellulose; Modified cellulose
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2301/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2401/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
- C08J2401/02—Cellulose; Modified cellulose
Definitions
- the present invention relates to nano-cellulose, its disper ⁇ sion in polymers and polymer precursors including epoxy and polyurethane (all in the following abbreviated as "polymers” or “polymer”) , and derived products such as nano-composites , adhesives, sealants, coatings.
- EP2928957A1 also WO 2014/087 053, METHOD OF MANUFACTURING A NANOCELLULOSE COMPOSITE, (Kalle Nattinen, VTT Finland, publ . 2015) describes the disadvantages and problems of prior art attempts of dispersing nano-cellulose in thermoset precursors, including: a) the necessarily high water content of nano-cel ⁇ lulose feedstock which in turn means a high energy demand for water removal, high transport costs etc., b) the formation of crystalline segments requiring expensive filtration and re ⁇ moval, alternatively re-dispersion using inefficient ultra- sound, and other practical problems.
- thermoset precursors such as epoxy or hardener using effi ⁇ cient milling equipment.
- the complete process from standard cellulose to nano-composites comprising nano-cellulose is thus possible without intermediate use of water.
- CA2549844A1 SOLID PHASE DISPERSION AND PROCESSING OF MICRO- AND NANO-CELLULOSIC FIBRES IN PLASTIC PHASE TO MANUFACTURE BIO-NANOCOMPOSITE PRODUCTS OF COMMERCIAL INTEREST (Sain Mohini M., publ 2014) discloses bio-nano-composite products using solid phase dispersion.
- the mechanical performance of the cel ⁇ lulose nanofibers is comparable to other engineering materials such as glass fibers, carbon fibers etc.
- a novel process for dispersion of plant stems (bundles of cellu ⁇ lose nanofibers with a diameter ranging between 10 to 70 nm and lengths of thousands of nanometers) has been developed to disperse cellulosic microfibres and nanofibres in solid phase into a molten plastic matrix or in a low viscosity water-based resin system in aqueous phase.
- the invention relates to manu ⁇ facturing Bio-nanocomposites of high performance by dispersing micro-and nano-cellulosic fibres into plastic matrix using conventional plastic processing equipment.
- This invention also overcomes one unique challenge of bio-nanocomposite pro ⁇ cessing, which is to make them commercially viable by surface modifying cellulosic micro-and nano-fibres derived from renew ⁇ able resources.
- US20160115359A1 WOOD ADHES IVES CONTAINING REINFORCED ADDI ⁇ TIVES FOR STRUCTURAL ENGINEERING PRODUCTS (Wang, Siqun, Univ. of Tennessee, publ. 2016) describes wood adhesives possibly including nano-cellulose, however, the disclosure is silent about special dispersion methods.
- the object of the invention is to produce thermosets compris ⁇ ing nano-cellulose.
- thermosets comprising well dispersed nano-cellulose.
- thermosets with improved properties such as increased impact resistance, increased tensile strength, and improved adhesion to various substrates .
- thermosets which is energy-efficient, economic and scalable .
- thermosets as composite articles, coatings, adhesives, sealants, and other end-uses .
- thermosets including epoxies and polyurethanes .
- the method to pro ⁇ cute thermosets including epoxies and polyurethanes comprising 0.1-10 % by weight nano-cellulose comprises the following steps :
- nano-cellulose is provided as water-bourne dispersion, optionally containing up to 50% ethanol, whereby said dispersion comprises at least 0.2%, preferably at least 0.3%, most preferably about 2-5% by weight nano-cellu ⁇ lose,
- nano-cellulose is intensively mixed with an or- ganic phase, specifically a thermoset precursor selected from epoxy, epoxy hardener, glycol and/or polyol, c) upon transfer of nano-cellulose to the organic phase, water and said optional ethanol are removed by distilla ⁇ tion at a temperature below 100 °C for minimising loss of reactive functionality of epoxy or polyurethane,
- the dry organic phase comprising nano-cellulose is mixed with the appropriate amount of reactive counterpart and optionally other desired additives, wherein said re ⁇ active counterpart is amine hardener for epoxies, and wherein said reactive counterpart is glycol or amine for polyisocyanate, and
- the final product is achieved following known curing procedures , said method further characterized by the fact that loss of re ⁇ active functionality of epoxy or polyurethane due to reaction with water is limited to ⁇ 50% of reactive epoxy or polyure ⁇ thane, preferably ⁇ 20% or ⁇ 10% or ⁇ 5% of reactive epoxy or polyurethane .
- said distil ⁇ lation is by speed distillation, preferably high-speed distil ⁇ lation.
- said distil ⁇ lation is by using a rotary evaporator and/or wiped film evap ⁇ orator .
- said distil ⁇ lation is by using a rotary evaporator.
- said distil- lation is by using a wiped film evaporator.
- said distil ⁇ lation is by using an extruder, including a planetary extruder with possibility for gas removal.
- said nano- cellulose is microfibrillar cellulose (MFC) and/or nanocrys- talline cellulose (NCC) .
- said nano- cellulose is selected from and shall be understood as cellulo ⁇ sic fibres, in particular cellulosic fibres obtained by de- fibering of lignocellulosic raw-material, optionally bleached, with typical fiber lengths of 10 nanometer up to 100 microme- ter, also comprising nanocrystalline cellulose (NCC) and mi ⁇ crofibrillar cellulose (MFC) .
- said epoxy compounds are selected from organic compounds carrying at least two epoxy functionalities, including bisphenol A adducts with epichlorohydrin .
- the residual water content in the polymer (e.g. epoxy) / cellulose mixture is reduced to below 10% by weight, preferably to below 3% and even more preferably to below 1% by treatment in a rotary evaporator, in a wiped-film-evaporator or in an extruder with possibility for gas removal, ideally under a pressure below 1 bar .
- carbon nano tubes are part of the composition, and where CNT may be dispersed e.g. by ultrasound separately in water and mixed thereafter with water/cellulose, or where CNT are dispersed in presence of cellulose, and where the final content of CNT in finished products may range from 0.1% by weight to 10% by weight,
- the loss of reactive functionality of epoxy or polyurethane due to reac ⁇ tion with water is compensated by adjusting the hardener reac- tion during curing, or by adding additional epoxy or diisocya- nate to ensure complete cross-linking, including reaction of e.g. diols formed by reaction of epoxy and water.
- the objects of the invention are also attained by a composi- tion produced according to the above mentioned preferred em ⁇ bodiments of the method.
- the composition comprises nano-cel- lulose and polymer selected from epoxy, epoxy hardener or pol- yurethane hardener such as glycol, optionally containing car ⁇ bon nano tubes and other functional additives including defoamers, pigments, antioxidants, viscosity adjusting chemi ⁇ cals and resins for adhesives.
- the objects of the invention are also attained by an article such as a composite article, a coating, an adhesive or a seal ⁇ ant based on the above mentioned preferred embodiments of the composition .
- the objects of the invention are also attained by use of a composition according the above mentioned preferred embodiment of the composition as a composite article, a coating, an adhe- sive or a sealant.
- thermosets including epoxies and polyurethanes com- prising 0.1-10 % by weight nano-cellulose, comprising the fol ⁇ lowing steps :
- nano-cellulose is provided as water-bourne dispersion, op ⁇ tionally containing up to 50% ethanol, whereby said dispersion comprises 0.2-10% by weight, preferably 0.3-5% nano-cellulose, b) said nano-cellulose is intensively mixed with an organic phase, specifically a thermoset precursor selected from epoxy, epoxy hardener, glycol and/or polyol,
- the function of various additives such as carbon nano tubes (CNT) for imparting e.g. electrical conductivity or microwave absorbancy, additional epoxy to guarantee cross-linking of side reaction products such as diols from the reaction of epoxy with water, and other additives is disclosed.
- CNT carbon nano tubes
- additional epoxy to guarantee cross-linking of side reaction products such as diols from the reaction of epoxy with water
- other additives is disclosed.
- the invention succeeds in provid ⁇ ing thermosets comprising well dispersed nano-cellulose with improved properties such as increased impact resistance, in ⁇ creased tensile strength, and improved adhesion to various substrates.
- the methods disclosed are energy-efficient, eco ⁇ nomic and scalable.
- nano-cellulose shall be understood as cellulosic fibres, in particular cellulosic fibres obtained by defibering of lignocellulosic raw-material, optionally bleached, with typical fiber lengths of 10 nanometer up to 100 micrometer, also comprising nanocrystalline cellulose (NCC) and microfibrillar cellulose (MFC) .
- NCC nanocrystalline cellulose
- MFC microfibrillar cellulose
- epoxy is defined as a raw material for epoxy composites, typically comprising bisphenol-A, bi- sphenol-F and related di- or polyfunctional compounds compris ⁇ ing epoxy groups (-CH2-COH2-) where the oxygen atom 0 and the two carbon atoms C form a reactive ring structure, said epoxy typically reacted with amines or other hardeners to cross- linked thermosets.
- Low molecular weight epoxy types such as epikote 235 were used in example 1. These are reaction products of CAS: 25068-38-6 NLP : 500-033-5 reg. nr. : 01-2119456619-26-0006, bisfenol-A and epichlorohydrin 50-100%, CAS: 9003-36-5 NLP: 500-006-8, reg nr: 01-2119454392-40-0003, Formaldehyde, oligo- meric reaction products with l-chloro-2 , 3-epoxypropane and phenol 25-50%,
- Viscosity 6-8000 mPas, epoxy equivalent 175 - 185.
- Epoxy and MFC were mixed and dispersed for 30 min at 3000 rpm using a Dispermill Yellow-Line dissolver. Residual water was removed by a) heating the mixture overnight in an oven at ca. 80 °C, b) by using a rotary evaporator, with vacuum at 40 °C, c) by using a wiped film evaporator under vacuum, d) by using an extruder with gas outlets for water removal.
- Reference sam ⁇ ples were prepared by mixing with water without nano- or mi ⁇ crofibrillar cellulose. The reaction of epoxy with water yielding a diol is the most significant loss reaction. The reaction of epoxy with OH groups in cellulose was found to be slow.
- Example 2 The final water content can approach zero, but for practical purposes about 1% water by weight or up to 3% is acceptable for most products.
- NFC and MFC were dispersed in water-soluble amines, partly wa ⁇ ter-soluble amines, amides as well as glycols as precursors for polyurethanes . It was not attempted to disperse cellulose in isocyanates as these chemicals react too fast with water. Curing of epoxy or diisocyanate with above mentioned hardener / cellulose mixtures proceeds as without cellulose addition, however, for water-soluble amines a shortened hardening time or pot life was observed.
- Carbon nano tubes were dispersed in water using ultra- sound using known procedures. Dispersed CNT were added to nano-cellulose in water, and the mixture was further dispersed in order to afford complexes of CNT and nano-cellulose. (CNT can also directly be treated with ultrasound in the cellulose- water mixture, however, the cellulose is exposed to high tem- peratures in that case.) Mixing said CNT/cellulose blend with epoxy results in a faster phase transfer of CNT/cellulose into epoxy compared with the phase transfer rate of pure cellulose. This is possibly due to the increased hydrophobicity of the CNT/cellulose complex. Following the general procedure out- lined in example 1, products result characterized by increased electrical conductivity and microwave absorbance.
- the weight ratio CNT / cellulose can be varied widely, e.g. between 5:95 to 95:5, but a 30:70 to 70:30 weight ratio is preferred.
- the total CNT content in the final formulation may be 0,1-10% or higher by weight where conductivity increases with increasing CNT content.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Nanotechnology (AREA)
- Manufacturing & Machinery (AREA)
- Dispersion Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Sealing Material Composition (AREA)
- Epoxy Resins (AREA)
- Polyurethanes Or Polyureas (AREA)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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US (1) | US11186689B2 (de) |
EP (1) | EP3580265B1 (de) |
CA (1) | CA3052918A1 (de) |
ES (1) | ES2929773T3 (de) |
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BR102020025922A2 (pt) * | 2020-07-28 | 2022-06-07 | Universidade Federal De Minas Gerais | Processo para obtenção de tinta de nanomateriais de carbono, produtos e uso em monitoramento de deformações, tensões e impacto |
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WO2009086141A2 (en) | 2007-12-20 | 2009-07-09 | University Of Tennessee Research Foundation | Wood adhesives containing reinforced additives for structural engineering products |
EP2300517B1 (de) * | 2008-07-17 | 2015-06-24 | Nanocyl S.A. | Verfahren zur herstellung eines verstärkten duroplast-polymerverbundstoffes |
CN102834448B (zh) * | 2010-04-01 | 2015-04-22 | 三菱化学株式会社 | 微细纤维素纤维分散液的制造方法 |
EP2613935B1 (de) | 2010-09-07 | 2016-12-07 | Yissum Research Development Company of the Hebrew University of Jerusalem Ltd. | Verbundstoffe auf cellulosebasis |
FI125900B (en) | 2012-12-04 | 2016-03-31 | Teknologian Tutkimuskeskus Vtt Oy | A process for preparing a nanocellulose composite |
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ES2929773T3 (es) | 2022-12-01 |
WO2018146338A1 (en) | 2018-08-16 |
US20190359779A1 (en) | 2019-11-28 |
US11186689B2 (en) | 2021-11-30 |
PL3580265T3 (pl) | 2023-01-02 |
CA3052918A1 (en) | 2018-08-16 |
EP3580265B1 (de) | 2022-09-07 |
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